Modified textile material resistant to penetration by aqueous media



United States Patent 3,410,720 MODIFIED TEXTILE MATERIAL RESISTANT T0 PENETRATION BY AQUEOUS MEDIA Charles A. Thomas, Ladue, and William Robert Hine, Jr., Kirkwood, Mo., assignors to Monsanto Company, St. Louis, Mo., a corporation of Delaware No Drawing. Filed July 12, 1965, Ser. No. 471,454 7 Claims. (Cl. 117-161) ABSTRACT OF THE DISCLOSURE This invention relates to the use of a composition comprising the reaction product of an epihalohydrin and an alpha-olefin/maleimide polymer in the preparation of textile materials having increased resistance to the penetration of aqueous media.

This invention relates to the chemical modification of textiles and textile fibers. More particularly, this invention provides textile materials having an increased resistance to the penetration of aqueous media and to a process for rendering such textile materials more water-repellent.

Unmodified natural and synthetic textile fibers and fabrics generally are not water-repellent. Water repellency is an unnatural but desirable property for them to have for many uses. Many textile treating compositions, both natural and synthetic, have been extensively used in the past. Many of these compositions are adequate for application under slightly acidic conditions, but are relatively inefficient under alkaline or neutral conditions. It is desirable, therefore, to find new methods and compositions for treating textiles under the varying chemical conditions found in the textile treating industry.

The purpose and object of this invention is to provide textile materials having improved water repellent characteristics. Another object and purpose is to provide a method for rendering a textile material more Water repellent with water dispersible, curable, nitrogen containing polymeric materials.

Briefly, the objects of this invention are accomplished by providing a textile material which has been rendered resistant to the penetration of aqueous media by treatment of the textile with an aqueous dispersion of the reaction product of an epihalohydrin and an alpha-olefin/ maleimide polymer, which polymer has been prepared by mixing a diamine having at least one primary amino group, with an alpha-olefin/maleic anhydride polymer, and heating the resulting reaction mixture to a temperature sufiiciently high to effect imidation of the polymer by the diamine. The textile material is rendered resistant to the penetration of aqueous media by treating the textile, i.e., applying to the textile the above reaction product dispersed in an aqueous medium, and allowing the treated textile thus obtained to dry until the water is substantially completely removed.

The textile materials which are made more resistant to the penetration by water by this invention includes not only woven fabrics but other related materials such as fibers, filaments, threads of natural and synthetic materials, as well as blends of natural and synthetic or mixed synthetic or mixed natural fibers used to make textile materials. Examples of textile materials which may be effectively treated include such natural fiber materials as cotton, wool, linen, and the synthetic fiber materials such as the superpolyamides, known generally as the nylons, the polyacrylonitrile fibers and fabrics, the polyester fiber materials, the modified cellulose materials such as rayon, and textile materials which are mixtures of any of the above such as cotton/polyester, polyacrylonitrile/wool, nylon/cotton textiles. Any suitable textile made for use exposed to natural rain, repeated washings, etc. such as awnings, suit cloth, shirts, sweaters, rainwear such as raincoats, hats, etc. may be treated effectively, with the reaction products described hereinbelow.

The alpha-olefin/rnaleic anhydride polymeric starting material used to make the products applied to textiles according to this invention may be low or high molecular weight polymers. Such molecular weights may range from about 2,000 up to about 225,000. Preferred polymers have molecular weights ranging from about 75,000 to about 125,000. Polymers having molecular weights which are too low provide less satisfactory textile treating agents whereas molecules of excessive: size introduce operational difliculties in the preparation of the textile treating polymeric product such as increased tendency to gel, and reduced ease of application to the textile.

The term alpha-olefin is used herein as a general term to designate organic olefinically"unsaturated compounds having the polymerizable double bond in the 1- position. It is only necessary that such compounds be polymerizable with maleic anhydride. Thus, this term includes alkyl and alkenyl vinyl ethers having an average of at least about 8 carbon atoms per alkyl or alkenyl group, the double bond of the alkenyl group not being in the alpha-position, omega-alkenoic acids having at least about 10 carbon atoms, styrene, chlorinated styrenes alkyl-substituted styrenes such as vinyl toluene, 4-ethylstyrene, as well as the simplealpha-olefin hydrocarbons. It is understood that mixtures of alpha-olefin materials such as mixtures of lower alpha-olefin hydrocarbons having from 2 to 8 carbon atoms with alpha-olefin materials of higher carbon content, say, up to 40 carbon atoms, or mixtures of alkyl vinyl ethers and alkyl-substituted styrenes may be used as the alpha-olefin for reaction with maleic anhydride. Branched and normal carbon atom chained alpha olefins may be used.

Although maleic anhydride is spoken of primarily as a comonomer with alpha-olefin in preparing the polymer starting material, we do so because maleic anhydride is preferred because of availability and cost considerations. Other equivalent polybasic carboxylic acid anhydrides could readily be' used to replace a part or all of the stoichiometric quantities of maleic anhydride in these polymers. Examples of such materials include itaconic acid anhydride, citraconic acid anhydride, aconitic acid anhydride, chlorinated maleic anhydride, or other polybasic unsaturated polymerizable acid or anhydride permissively containing substituents which do not interfere in the polymmerization reaction. The invention thus contemplates the use of polymer materials made from two or more monomers, but which, for convenience will be referred to as alpha-olefin/maleic anhydride polymers.

These alpha-olefin/maleic anhydride polymer starting materials are usually prepared in an aromatic solventnon-solvent such as benzene, toluene, xylene, etc., by reacting the alpha-olefin and the maleic anhydridein the molar proportions desired in the polymer which may range from about 0.9:1 to about 1.8:1 of maleic anhydride to the alpha-olefin, in the presence of suitable catalysts such as azobis(isobutyronitrile), di-tert-Ibutyl peroxide, dibutyl perbenzoate, butyl peroxide, etc.., at temperatures which may range from about 50 C. to C. Preferred polymers are those containing from about 0.95:1 to about 1.05:1 of maleic anhydride to alpha-olefin. The better polymers appear to be those having a high ratio of alternating maleic anhydride to alpha-olefin units, which is generally obtained by adding the maleic anhydride to the reaction mixture containing the alpha-olefin over a l to 4 hour period. The polymeric alpha-olefin/maleic anhydride solvent system is usually heated] to a temperature high enough to remove most of the reaction solvent and then the polymer is prepared for reaction with the diamine, usually by adding to the polymer reaction mixture a suitable diluent to replace the aromatic solvent or to form an azeotrope therewith during the heating step. Alcohols which are preferred are n-butanol, isobutanol, n-propanol, 2-butoxyethanol, or similar alcohol mixtures boiling in about the same range.

The diamine or diamine mixtures used in the formation of the polymeric imides can vary considerably in structure and reactivity. It must have at least one primary amino group. It is preferably an aliphatic diamine but it may contain more than two amino groups and may be an aromatic diamine such as 1,4-phenylenediamine, N,N- dimethyl-1,4-phenylenediamine, etc. However, it is preferred to employ at least one diamine of the structure wherein R and R, which may be like or un-like, are hydrogen, alkyl groups containing 1 to 4 carbon atoms, or aralkyl groups having from 7 to 10 carbon atoms, and R" is an alkylene radical containing at least 2 carbon atoms and generally not greater than about carbon atoms. The diamine compounds can be substituted or unsubstituted. When substituents are present it is only necessary that they be less reactive with the anhydride than is the primary amino group, and that they are not alpha to the nitrogen atom. Suitable non-interfering substituents which may be present include cyano, acetyl, aryl, benzoyl, tert-amino, ether groups, sulfonyl, arylthio, alkylthio, and the like.

It is generally preferred that neither R nor R' in the above preferred structure be hydrogen. Thus the preferred amines are tertiary amines at that point. The use of tertiary amines containing the primary amino group reduces to a minimum the possibility of cross-linking of the polymer prior to reaction with the epoxy compound as described hereinafter. We prefer that the diamine reactant or mixture of diamines contain at least about 50 mol percent of dimethylamino groups. In some instances, a secondary or even a primary amine can be employed to advantage in preparing the compounds of the present invention. Also, amines of the above type can be partially replaced with various other amines and amideforming compounds, such as Duomeen T, 'butylamine, otlitadecylamine, various soluble ammonium salts, and the li e.

Although it is preferable to use N,N-dimethylaminoalkylene amines, and particularly, N,N-dimethyl-l,3- propanediamine, numerous other diamines corresponding to the above general formula are suitable for use in place of or in admixture with these prefered diamines in preparing the present textile treating materials. Representative members of this group of diamines include, for example, N,N-dimethylethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, N-hydroxyethylethylenediamine, N hydroxypropylethylenediamine, N hydroxypropylpropylenediamine, N-hydroxypropyl-1,3-propanediamine, N-hydroxypropyl-l,6-hexanediamine, N-hydroxypropyl-Z- oxa 1,6 hexanediamine, N-Z-aminoethylpiperazine and N-3-aminomethylpyridine.

In conjunction with tertiary substituted diamines such as N,N-dimethyl-l,3-propanediamine, minor amounts (up to about 20 mol percent) of unsubstituted polyamines may be substituted in order to attain a higher viscosity in the product. Representative polyamines include ethylenediamine, propylenediamine, 1,6-hexanediamine, diethylenetriamine, iminobispropylamine, triethylenetetramine, and tetraethylenepentamine.

The alpha-olefin/maleic anhydride cop-olymer is mixed with the diamine or diamine mixture, preferably with agitation, in the presence of a suitable organic aromatic hydrocarbon alcohol mixture and then heated to a temperature sufiiciently high to effect imidation of the polymer and distillation of some of the solvent mixture. Using a .4 mixture of N,N-dimethylamino-1,3-propane diamine and N-(Z-hydroxyethyl)ethylenediamine mixed in with the copolymer in an amount which is equivalent to between about 0.9 to 1 mole of the maleic anhydride content of the copolymer, heating up to about -l50 C. for from 0.75 to 2 hours is sufiicient to effect imidation of the polymer.

The polymeric imide-amine thus obtained is reacted with an epihalohydrin preferably in the presence of a xylene-alcohol-water mixture to form the polymeric alphaolefin/maleimide haloalkanol reaction product. In the interest of convenience and economy, it is generally preferred to use epichloro-hydrin in this capacity. However, other epihalohydrins can also be used. The reaction between the epihalohydrin and the polymeric imide-amine can be conveniently carried out at substantially room temperature by adding an appropriate amount of the epihalohydrin to a solution of the polymeric imide in xylene in a conventional water-lower alkanol-xylene reaction mixture such as butanol, ethoxyethanol, butoxyethanol, a butoxy carbitol, and the like, followed by dilution with water. Since the reaction is not instantaneous, the amount of the epoxide of the epihalohydrin entering the reaction can be controlled by the reaction time as well as by the amount of the epoxide added to the mixture. Although the reaction progresses slowly in the absence of appreciable water, it is catalyzed and proceeds quite rapidly upon the addition of water. When water is added, the aqueous mixture originally becomes somewhat turbid. This turbidity of the aqueous reaction mixture may be dissipated, if desired, by diluting the reaction product with water-2-propanol or similar alcoholic mixtures. The resulting clear solution can then be diluted with additional water to any desired concentration. A portion of the epoxide is hydrolyzed in the aqueous system to the corresponding glycol. The epoxide content of the polymeric product is normally somewhat less than the quaternary amine content obtained by reaction of the polymeric imide with the epihalohydrin. The degree of hydolysis of the epihalohydrin or other epoxide can be controlled within limits by controlling alkalinity and by other well-known methods, thus providing an additional means of tailoring the properties of the product.

Although sufiicient epoxide can be made available to react with all of the amine groups in the polymer, it is preferred that the polymeric compounds contain some free amino groups together with the quaternary groups. In general, the numerical ratio of epoxide groups, including hydrolyzed epoxides, to cyclic imide groups can vary between about 0.1:1 and 1:1. It is preferred to maintain this ratio between about 0.3:1 and about 0.9:1.

The polymeric haloalkanol compounds thus obtained have a relatively short shelf life since they are subject to cross-linking and gelation upon standing or heating. In order to stabilize them in a convenient, commercially available form they are preferably treated with an acid, preferably a hydrohalidic acid, either alone or in combination with other mineral acids such as phosphoric, sulfuric and the like. Alternately, the compounds may be stabilized with a mineral acid composition containing no hydrohalidic acids. Such stabilizing acids neutralize amino groups present, but do not add to the epoxides. When substantially halide-free acid compositions are used for stabilization, some halide ion is present due to the epihalohydrin in the system, and adds to the epoxides. In any event, suflicient halide ion must be present to effect stabilization of the epihalohydrin groups in the product. This treatment with the hydrohalidic acid converts any polymeric epoxyalkyl groups to the corresponding haloalkanol form. These polymeric alkanols which are usually prepared in 10 to 40% polymer solids solutions are stable for long periods of time, and thus can be subjected to normal shipping and storage without any danger of any extensive cross-linkage or consequent gelation.

It will generally be preferred to at least dilute with water the acid stabilized polymeric alkanols to a concentration desired for textile treating purposes. With some of these polymeric materials it may be desirable to neutralize the acidified polymeric alkanol solution or suspension with a base to a higher pH for application to the textile. With the lower molecular weight materials, say, those derived from imides of maleic anhydride copolymers having viscosities below about 0.6 at a concentration of four (4) times 1 percent in methyl ethyl ketone a strong base pretreatment to raise the pH of the mixture to pH 9 to 11, with neutralization within about to minutes to pH 6 to 8 with an acid may be desirable to enhance the water-proofing character of these polymeric materials. When appropriate, the base treatment is usually done after the acidified polymeric solution has been diluted with water to the approximate percent polymer solids concentration for use for textile treatment. Useful bases which may be used include the alkali metal and alkaline earth metal oxides, and hydroxides such as sodium and potassium oxides, sodium hydroxide, potassium hydroxide, calcium oxide, calcium hydroxide, magnesium hydroxide, ammonia, ammonium hydroxide, organic nitrogen bases etc. The alkali metal and alkaline earth metal bases of higher atomic weight could be used but are not practical in an economic sense. The preferred bases are sodium hydroxide, potassium hydroxide, dissolved in water.

This base treatment appears to make these lower molecular weight materials more eflicient. The higher molecular weight products, i.e., those derived from polymer maleimides having viscosities about 0.6 (4 times 1% of polymer in methyl ethyl ketone) generally do not need the strong base pretreatment before use.

In determining how much of the polymeric reaction product to use in water for the particular textile to be treated we have found that the better practice for this invention is to measure the textile treatment by the weight percent of polymeric reaction product in the aqueous textile treating solution rather than the weight percent pickup by the treated textile. This is because some textiles have such a small weight percent difference before and after treatment, and since some textiles are synthetic chemical in nature that chemical analysis of the treated sample does not give a sufficiently accurate indication of the amount of water repellent character imparted to the textile. Generally, aqueous solutions containing from about 0.5 to about 50% of polymeric alpha-olefin/ maleimide-epihalohydrin reaction product solids in water based on the weight of the textile being treated therewith are used:

Based upon the best information currently available, the active textile treating compositions of the present invention are believed to be polymeric epoxyalkylammonium salts containing randomly recurring units of the following illustrative structures when the alpha-olefin moiety of the polymer starting material is derived from an alpha-olefin hydrocarbon:

wherein R and R can be hydrogen, alkyl groups containing up to 4 carbon atoms, and aralkyl groups containing up to 10 carbon atoms,

A is chloride, bromide or iodide,

r is a whole number from 2 to 20,

t is a positive whole number up to about 40, and

x and y are numbers greater than 0, the preferred ratio of y to at being at least about 1:1.

Since the present polymeric sizes preferably contain free amino groups and can also contain non-epoxy quaternary groups, the following illustrative formula illustrates the type of randomly recurring units that may be present:

R, R, A, r and thave the above-assigned values,

R is an alkyl or a monoor dihydroxy alkanol group containing 1 to 3 carbon atoms or an aralkyl group containing 7 to 10 carbon atoms, and

x y, z and s are whole numbers, with s being between 0 and about 75% of the sum of y, z, and s; y being equal to at least about 10% of said sum, and the ratio of said sum to at being at least about 1:1.

As pointed out above, this type of textile treating agent has a propensity to cross-link and to form a gel after preparation. Therefore, they are usually converted to the corresponding alcohols, or more precisely the corresponding 1substituted-2-alkanols, by stabilization with a hydrohalidic acid, particularly hydrochloric acid to prevent premature gelation. It is not necessary to convert all of the quaternary ammonium salts to the corresponding alkanols, but it is only required that the stabilized form of the composition contain a preponderant proportion of the alcohols. The stabilized textile treating agent obtained by the acidification is believed to be a polymer having randomly recurring units of the following illustrative structures:

wherein R, R, A, r, t, x and y have the above-assigned values, and Y is chloride, bromide or iodide.

The water-proofing of the textile may be accomplished according to this invention by impregnating the textile material with a solution of the alpha-olefin/maleimide haloalkanol or epoxyalkyl reaction product in an appropriate solvent or dispersion medium, which is preferably aqueous, and then volatilizing off the solvent. For example, the wetted textile may be dried in an oven which includes curing of the resinous material to produce substantial water resistance on the textile.

The textile material may be dipped or immersed in a solution or dispersion of the polymeric haloalkanol or epoxyalkyl reaction product and the textile may be left in such solution or dispersion for a time sufiicient for the textile to absorb or pick up the desired amount of polymer, termed the percent of pickup of polymer after drying of the treated textile. The composition may be dripped or sprayed on the textile until the textile is wetted out with the solution. After the immersion, drip or spray treatment the amount of polymer absorbed or adsorbed by the textile can also be controlled by padding, wringing, squeezing or hydroextracting the wet treated textile. In general, the procedure followed will be dictated by the desire to have from about 0.01% to about 5% by weight, based on the dry textile material, of the polymer product on the textile. Good practical water repellent effects are obtained on most textile with the application of from about 0.1 to about 2% by weight, on the dry textile material.

After the polymeric compounds have been applied, the wetted textile material may then be dried either at ambient temperatures or more quickly in standard drying operations which may include heating up to 250 to 360 F. to obtain a cure or water repellent finish on the textile material. The duration of the heating may var widely depending primarily on the liquid content and the temperature used but is generally between about 1 and 30 minutes. The textile material thus obtained may be given the usual finishing operations such as refinish wash to remove water soluble materials, steam framing, and the like.

The solutions or aqueous dispersions of the above polymeric reaction products may also contain other textile auxiliaries such as stiffening or bodying agents, softening agents, curing agents, wetting agents, antifoaming agents, and the like, but such agents are not essential to this invention.

The invention and the manner in which it accomplished its objects will be more readily understood by reference to the following detailed description of preferred embodiments thereof. In these examples and throughout the application, all proportions are expressed in parts by weight unless otherwise indicated.

EXAMPLE 1 This example illustrates a method by which the material used in this invention for modifying the properties of the textile is prepared.

A mixture of about 380 grams (1.5 moles) of l-octadecene in 50 moles of butyl acetate was warmed to about 135 C. in a 1-liter flask under an atmosphere of carbon dioxide. Then 2.5 ml. (0.0135 mol) of di-tert-butyl peroxide was added, followed by the slow addition, with continuous stirring during a" period of 2% hours, of a warm (4050 C.) solution of approximately 147 grams (1.5 mol) of maleic anhydride and 2.5 ml. (0.0135 mol) of di-tert-butyl peroxide in 200 ml. of butyl acetate. The temperature of the reaction mixture was maintained at about 135 C. for approximately 4 hours, at which time the infrared spectrum of the polymeric solution showed that all the maleic anhydride was consumed. The temperature was then raised to about 200 C. while butyl acetate was distilled out, and the pressure was gradually lowered to about 40 mm. of mercury, resulting in recovery of substantially all the butyl acetate. The pressure was then reduced further to about 2-3 mm. of mercury to recover 60.5 grams of unreacted olefin at a final flask temperature of 210 C. The residue of polymer weighed about 463 grams. Since a negligible amount of maleic or succinic anhydride distilled out, the average ratio of olefin to maleic anhydride in the polymer was about 0.84. The specific viscosity of the alpha-olefin/maleic anhydride copolymer at 4% concentration in methyl ethyl ketone was 0.34, corresponding to a molecular weight of about 4,400.

A solution of about 30.9 grams of the above polymer (containing 0.1 mol of anhydride) in 30 ml. of xylene mixed with 2-butoxy-1-ethanol was treated dropwise at approximately 140 C. with about 10.2 grams (0.1 mol) of N,N-dimethyl-1,3-propanediamine. The mixture was held at a reflux temperature of 140 C. for 2 hours while the water of reaction was distilled off. The temperature was then raised to about 155 C. to remove most of the xylene, the remainder being removed by codistillation with 2-butoxyethanol. The residue, about 66 grams of a 2- butoxyethanol solution of the polymeric imide, was cooled to 24 C. To this solution were added about 8 ml. (0.1 mol) of epichlorohydrin and ml. of water. The resulting cloudy suspension warmed to about 30 C. and became clear in about minutes. An additional 20 ml. of water was added gradually during the next 20 minutes at 30-32 C. The mixture remained completely clear uponfurther addition, and 15 ml. of water and about 10 ml. of concentrated HCl were added gradually while the pH was held between about 3 and 4. It was furtherdiluted to about 420 grams, and an additional 0.7 gramof con-. concentrated HCl added.

EXAMPLE 2 about C. in an inert atmosphere. Then equimolar:

amounts of 3-dimethylarninopropylarnine and N-(2-hy-.

droxyethyl)ethylenediamine were added in amounts-sufii-.

cient to provide for substantially complete stoichiometric. imidation of the anhydride equivalent of the copolymer. The imidation reaction was accomplished by heating the resulting mixture under reflux over an hour period with a terminal temperature of about C. The aminoimide copolymer thus obtained was reacted with epichlorohydrin and then stabilized with hydrochloric acid in the same manner described in connection with Example 1.

For the following examples tridecyl vinyl ether/maleic anhydride copolymers having specific viscosities of about 1.80 were treated with a 1:1 mole ratio mixture of N,N-.. dimethylamino-1,3-propanediamine and N- (2-hydroxyethyl)ethylenediamine, and heated in xyleneisobutanol solvent to about 130 C. to obtain a polymeric tridecyl vinyl ether/maleimide polymer therefrom, which was treated with sufficient epichlorohydrin in water-2-propanol-xylene mixture to obtain water dispersible polymeric products, stabilized with hydrochloric acid having between about 29.5 and 30.4 chlorohydrin equivalent. The samples were diluted to 1% concentration, adjusted to the desired pH with aqueous sodium hydroxide and used as the test solutions for treating the test fabric materials described in the following examples.

EXAMPLE 3 Samples of light and heavy polyacrylonitrile fabrics, rayon/stretch nylon blend fabrics, and polyacrylonitrile/wool blend fabrics, were soaked for 15 minutes in aqueous 1 percent polymer solids solutions of tridecyl vinyl ether-maleimide-epichlorohydrin polymeric reaction products prepared as described above, having the pH, thereof adjusted to 7.5. The treated fabrics were dried on a Noble and Wood Dryer at 214 F. for 130 seconds, and cured for 15 minutes at 220 F. and then for 10 minutes at 300 F. The cured treated fabrics thus obtained were tested according to the standard Water RepellencyzSpray Test Standard Test Method 22-1961 (American Society for Testing and Materials Designation; D583-58). The light weight polyacrylonitrile and rayon/nylon fabrics showed only partial wetting of the upper surface. The heavier polyacrylonitrile fabric showed only slight random sticking of water particles to the upper surface. The polyacrylonitrile/wool (55-45) blend fabric showed wetting on the upper surfaces only at the spray points. Similar but untreated light and heavy weight polyacrylonitrile, ray-..

on/stretch nylon, and polyacrylonitrile/wool blend fabrics in the same spray tests show complete wetting of the" upper and lower fabric surfaces.

EXAMPLE 4 Cotton fabric samples were treated with two samples of a tridecyl vinyl ether/maleimide-epichlorohydrin poly-. meric reaction product prepared as described in Example 2, and diluted with water and treated 'with aqueous Dabco triethylenediamine to adjust the pHs to 7.4 and 8.2 respectively. The treating solutions contained about 0.6% of the polymeric reaction products. With these samples the weight percent pickup was determined by use of nitrogen analysis. The samples contained 1.44 and 1.43 weight percent pickup of the polymeric material. After curing and test sprayed as described in Example 3, the upper surfaces of the treated cotton were wetted but not the lower surfaces. Untreated control samples of cotton sprayed in the same manner are wetted throughout.

We claim:

1. A textile material which has been rendered resistant to penetration by aqueous media by treatment of the textile with the reaction product of an epihalohydrin and an alpha-olefin/maleimide polymer, which polymer has been prepared by mixing a diamine having at least one primary amino group with a copolymer of an alpha olefin having an average of from 2 to 40 carbon atoms and maleic anhydride, the molar ratio of the anhydride to the alphaolefin in the copolymer being from about 0.921 to about 1.821, and heating the resulting mixture until an alphaolefin/maleimide polymer is formed, wherein the ratio of epoxide groups to cyclic imide groups in the reaction product is between about 0.1:1 and 1:1.

2. A textile material rendered resistant to penetration by aqueous media as described in claim 1 wherein the reaction product of the epihalohydrin and the alpha-olefin/ maleimide polymer is treated with an alkaline material prior to treatment of the textile with said reaction product.

3. A textile material rendered resistant to penetration by aqueous media by treatment of the textile with the reaction product of an epichlorohydrin and an alkyl vinyl ether/maleimide polymer, said polymer having been prepared by mixing a dialrnine having at least one primary amino group with a copolylrner of an alkyl vinyl ether having an average of at least about 8 carbon atoms in said alkyl groups and maleic anhydride, the molar ratio of the anhydride to the alkyl vinyl ether in the polymer being from about 0.9:1 to about 1.811, and heating the resulting mixture to form the alkyl vinyl ether/maleimide-polymer therefrom, wherein the ratio of epoxide groups to cyclic imide groups in the reaction product is between about 0.1:1 and 1:1.

4. A textile material rendered resistant to penetration by aqueous media as described in claim 3 wherein the reaction product is obtained by reacting epichlorohydrin with a tridecyl vinyl ether/maleimide polymer, 'which polymer is prepared by mixing a tridecyl vinyl ether/maleic anhydride polymer, the molar ratio of the anhydride to the tridecyl vinyl ether in the polymer being from about 0.9:1 to about 1.8:1, with a diarnine having at least one primary amino group and heating the resulting mixture to form the tridecyl vinyl ether/maleimide polymer therefrom, wherein the ratio of epoxide groups to cyclic imide groups in the reaction product is between about 0.121 and 1:1.

5. A method of rendering a textile material resistant to penetration by aqueous media which comprises applying to said textile the reaction product of an epihalohydrin and an alpha-olefin/maleimide polymer, which polymer has been prepared by mixing a diamine having at least one primary amino group with a copolymer of an alphaolefin having an average of from 2 to 40 carbon atoms and maleic anhydride, the molar ratio of the anhydride to the alpha-olefin in the copolymer being from about 0.921 to about 1.8 1, and heating the resulting mixture to form the alpha-olefin/maleimide polymer, wherein the ratio of epoxide groups in the reaction product is between about 0.1:1 and 1:1.

6. A method as described in claim .5 wherein the reac tion product applied to said textile is the reaction product of an epihalohydrin and an alkyl vinyl ether/maleimide polymer, said polymer having been prepared by mixing a diamine having at least one primary amino group with a copolymer of an alkyl vinyl ether having an average of at least 8 carbon atoms in said alkyl groups and maleic anhydride, the molar ratio of the anhydride to the alkyl vinyl ether in the polymer being from about 0.9:1 to about 1.8 1, and heating the resulting mixture to form the alkyl vinyl ether/maleimide polymer therefrom, 'wherein the ratio of epoxide groups to cyclic imide groups in the reaction product is between about 0.1 :1 and 1:1.

7. A method as described in claim 6 wherein the reaction product applied to said textile is the reaction product of epihalohydrin and a tridecyl vinyl ether/maleimide polymer, which polymer is prepared by mixing a mixture of N,N-dimethylamino 1,3-propanediamine and N-(2-hydroxyethyl)ethylenediamine with a tridecyl vinyl ether/ maleic anhydride polymer, and heating the resulting mixture to form the tridecyl vinyl ether/m aleimide polymer therefrom.

References Cited UNITED STATES PATENTS 2,160,375 5/1939 VOsS. 2,469,407 5/ 1949 Powers et al 117-161 2,616,867 11/1952 Rossin 117-139.5 X 3,150,112 9/1964 Toy 26080.76 X 3,181,969 5/1965 Wakeman 117-1395 X FOREIGN PATENTS 713,142 7/1965 Canada.

WILLIAM D. MARTIN, Primary Examiner.

M. R. P. PERRONE, Assistant Examiner. 

